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CN1118610A - Zinc powder for alkaline batteries - Google Patents

Zinc powder for alkaline batteries Download PDF

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Publication number
CN1118610A
CN1118610A CN94191302A CN94191302A CN1118610A CN 1118610 A CN1118610 A CN 1118610A CN 94191302 A CN94191302 A CN 94191302A CN 94191302 A CN94191302 A CN 94191302A CN 1118610 A CN1118610 A CN 1118610A
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powder
contain
zinc
500ppmin
arbitrary
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CN1045999C (en
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I·A·斯特劳温
M·L·米乌斯
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Umicore NV SA
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Union Miniere NV SA
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • H01M4/42—Alloys based on zinc
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Battery Electrode And Active Subsutance (AREA)
  • Primary Cells (AREA)

Abstract

A powder for use in an alkaline battery, the composition of which is: or (1), 1-95 ppm Al; one of 0.001-2% Bi, 0.005-2% In and 0.003-2% Pb; optionally 0.003-2% Ca; or (2), 1-95 ppm A; 0.001-2% Bi; 0.005-2% In; optionally 0.003-2% Pb; or (3), 1-95 ppm Al; one of 0.001-2% Bi and 0.005-2% In; 0.003-2% Pb, optionally 0.003-2% Ca; or (4), 1 to 1000ppm Li; 0.001-2% of Bi and 0.005-2% of In, optionally 0.003-2% of Ca; or (5), 1 to 1000ppm Li; 0.003-2% Pb, 0.003-2% Ca, optionally 0.005-2% In; or (6)1 to 1000ppm Li; 0.001-2% of Bi, 0.003-2% of Pb, optionally 0.005-2% of In and 0.003-2% of Ca; or (7), 1 to 95ppm Al; 1-1000 ppm Li; 0.001-2% of Bi, 0.005-2% of In and 0.003-2% of Pb, optionally 0.003-2% of Ca; the remainder being zinc and unavoidable impurities present in the above metals, except that these powders contain calcium, excluding indium-containing powders having an aluminum content of 50ppm in the mixed compositions (1) and (3).

Description

用于碱性电池的锌粉Zinc powder for alkaline batteries

本发明涉及用于碱性电池的含铝和/或锂的锌粉。The present invention relates to aluminum and/or lithium containing zinc powders for use in alkaline batteries.

由EP-A-0427315已知含铝锌粉。在其文件中，要求保护的是用于碱性电池的锌基粉末，其特征在于其含有0.005-2％的铝，以及Aluminum-containing zinc powders are known from EP-A-0427315. In its document, what is claimed is a zinc-based powder for alkaline batteries, characterized in that it contains 0.005-2% aluminum, and

或含0.0001-0.01％REM，REM为一种稀土金属或稀土金属混合物；Or contain 0.0001-0.01% REM, REM is a rare earth metal or mixture of rare earth metals;

或除锌和不可避免的杂质外，仅含0.0001-2％至少一种铟和REM；or containing only 0.0001-2% of at least one of indium and REM other than zinc and unavoidable impurities;

或除锌和不可避免的杂质外，仅含0.003-2％铋和0.0001-2％至少一种铟和REM；or containing only 0.003-2% bismuth and 0.0001-2% at least one of indium and REM, in addition to zinc and unavoidable impurities;

或除锌和不可避免的杂质外，仅含0.005-2％铅和0.0001-2％至少一种铟和REM；or containing only 0.005-2% lead and 0.0001-2% at least one of indium and REM, other than zinc and unavoidable impurities;

或除锌和不可避免的杂质外，仅含0.005-2％铅，0.003-2％铋和0.0001-2％至少一种铟和REM。Or only 0.005-2% lead, 0.003-2% bismuth and 0.0001-2% at least one kind of indium and REM in addition to zinc and unavoidable impurities.

在其文件中的第一个实例涉及一种粉末，它是通过雾化一种其组成如下的熔融体而制得的：220ppmAl，5ppmLa，12ppmCe，500ppmPb，54ppmIn，其余为经热致精炼的锌。第二个实例涉及另一种由雾化其组成如下的熔融体而制得的粉末：600ppmAl，500ppmPb，500ppmBi，100ppmIn，其余为经热致精炼的锌。其它所有给出的实例均涉及铝含量从0.03％至最高达0.06％(在本文中给出的所有百分数均指重量百分数)的粉末。The first example in its documentation concerns a powder produced by atomizing a melt with the following composition: 220ppm Al, 5ppmLa, 12ppmCe, 500ppmPb, 54ppmIn, balance thermally refined zinc . The second example concerns another powder obtained by atomizing a melt having the following composition: 600 ppm Al, 500 ppm Pb, 500 ppm Bi, 100 ppm In, the remainder being thermally refined zinc. All other examples given relate to powders with an aluminum content ranging from 0.03% up to 0.06% (all percentages given here refer to weight percentages).

由这些实例得到的粉末其共性在于：它们均至少含有约200ppm的Al以及在电池部分放电之前和之后，它们在电池的电解质中具有优良的耐腐蚀性。然而，它们也有短处：在某些类型的电池中，其中包括LR6-型和较小类型电池中，它们可能引起短路。The powders obtained from these examples have in common that they all contain at least about 200 ppm Al and that they have excellent corrosion resistance in the electrolyte of the battery before and after partial discharge of the battery. However, they also have a disadvantage: they can cause short circuits in certain types of batteries, including LR6-type and smaller types.

本发明的目的在于为碱性电池提供一种含铝和/或锂的锌粉，与由EP-A-0427315中实例中得到的粉末相比，它在仍具有足够的耐腐蚀性的同时，不造成短路或在很大程度内不造成短路现象。The object of the present invention is to provide an aluminum and/or lithium containing zinc powder for alkaline batteries which, compared to the powders obtained in the examples in EP-A-0427315, while still having sufficient corrosion resistance, Do not cause short circuits or do not cause short circuits to a large extent.

按照本发明制得的粉末，其特征在于它有如下组成形式：The powder obtained according to the present invention is characterized in that it has the following composition forms:

或者是(1)，1-95ppmAl；0.001-2％Bi、0.005-2％In以及0.003-2％Pb中的一种；以及任选加入0.003-2％Ca；Or (1), 1-95ppmAl; one of 0.001-2%Bi, 0.005-2%In and 0.003-2%Pb; and optionally adding 0.003-2%Ca;

或者是(2)，1-95ppmAl；0.001-2％Bi；0.005-2％In；以及任选加入0.003-2％Pb；Or (2), 1-95ppm Al; 0.001-2% Bi; 0.005-2% In; and optionally 0.003-2% Pb;

或者是(3)，1-95ppmAl；0.001-2％Bi和0.005-2％Zn中的一种；0.003-2％Pb以及任选加入0.003-2％Ca；Or (3), 1-95ppmAl; one of 0.001-2% Bi and 0.005-2% Zn; 0.003-2% Pb and optionally 0.003-2% Ca;

或者是(4)，1-1000ppmLi；0.001-2％Bi和0.005-2％In中的至少一种，以及任选加入0.003-2％Ca；Or (4), 1-1000ppmLi; at least one of 0.001-2% Bi and 0.005-2% In, and optionally adding 0.003-2% Ca;

或者是(5)，1-1000ppmLi；0.003-2％Pb，0.003-2％Ca以及任选加入0.005-2％In；Or (5), 1-1000ppmLi; 0.003-2%Pb, 0.003-2%Ca and optionally 0.005-2%In;

或者是(6)，1-1000ppmLi；0.001-2％Bi，0.003-2％Pb以及任选加入0.005-2％In和0.003-2％Ca中的至少一种元素；Or (6), 1-1000ppmLi; 0.001-2% Bi, 0.003-2% Pb and optionally adding at least one element in 0.005-2% In and 0.003-2% Ca;

或者是(7)，1-95ppmAl；1-1000ppmLi；0.001-2％Bi、0.005-2％In和0.003-2％Pb中的至少一种，以及任选加入0.003-2％Ca；Or (7), 1-95ppmAl; 1-1000ppmLi; at least one of 0.001-2%Bi, 0.005-2%In and 0.003-2%Pb, and optionally adding 0.003-2%Ca;

其余的是锌以及上述金属中存在的不可避免的杂质，但除非这些粉末含钙，否则排除混合组成(1)和(3)中铝含量为50ppm的含铟粉末。The remainder is zinc and unavoidable impurities present in the above metals, but unless these powders contain calcium, indium-containing powders with an aluminum content of 50 ppm in mixed compositions (1) and (3) are excluded.

事实上，关于本发明粉末中的铝，本申请人发现与EP-A-0427315中实例粉末相反，那些具有低Al含量的粉末在电池中使用时，不产生或很少产生短路现象。同时，本发明人也发现(这将在其后得到证明)，很低的Al含量给予粉末以足够的耐腐蚀性，尤其是在电池部分或完全放电后。其它合金元素(Bi和/或Pb和/或In)在放电前给予粉末以足够的耐腐蚀性。这样，此种粉末适于制作任何类型的碱性电池，例如LR6，LR14，LR20等等。In fact, with regard to the aluminum in the powders of the present invention, the Applicant has found that, contrary to the powders exemplified in EP-A-0427315, those powders with a low Al content produce no or very little short circuiting when used in batteries. At the same time, the inventors have also found (as will be demonstrated later) that a very low Al content gives the powder sufficient corrosion resistance, especially after the battery has been partially or completely discharged. Other alloying elements (Bi and/or Pb and/or In) give the powder sufficient corrosion resistance before discharge. Thus, this powder is suitable for making any type of alkaline battery, such as LR6, LR14, LR20, etc.

另外，本申请人还发现在部分或完全放电后，在对气体逸出方面的影响方面锂与铝相类似。因此这两种元素能单独或一起使用。In addition, the applicant has also found that lithium is similar to aluminum in its effect on gas evolution after partial or full discharge. These two elements can thus be used alone or together.

这里，应该注意以下几点：EP-A-0457354涉及的碱性电池锌粉中包括那些含0.01-1％In，总量为0.005-0.5％的Pb和Bi中的一种或两种以及总量为0.005-0.2％的Li、Ca和Al中的一种或多种的锌粉。给出了许多种不同组成的粉末实例：不含Al的粉末，含Al≥0.01％的粉末以及含25ppmAl的粉末，但它们与本发明的粉末不同，因为它们含Ca、In、Bi以及任选加入的Pb。没有给出含锂粉末的实例。但叙述了锂与铝有相似的影响。在其文件中没有提到当高铝含量时会引起短路问题，也没有提到此难题可通过限制铝含量为1-95ppm，在不损害粉末的耐腐蚀性的情况下得以解决。Here, the following points should be noted: EP-A-0457354 relates to zinc powder for alkaline batteries, including those containing 0.01-1% In, one or both of Pb and Bi and the total amount of 0.005-0.5% Zinc powder of one or more of Li, Ca and Al in an amount of 0.005-0.2%. Many examples of powders of different compositions are given: powders without Al, powders with Al ≥ 0.01% and powders with 25 ppm Al, but they are different from the powders of the invention because they contain Ca, In, Bi and optionally Added Pb. No examples of lithium-containing powders are given. Lithium, however, is described to have similar effects as aluminum. There is no mention in its document that high aluminum content will cause short circuit problems, nor that this problem can be solved by limiting the aluminum content to 1-95ppm without compromising the corrosion resistance of the powder.

JP-A-62176053公开了一种汞齐化锌粉，其含0.001-0.5％In，0.005-0.5％Pb，0.005-0.5％Al，0.005-0.5％的一种或多种Tl、Sn、Cd和Ga，0.0001-0.5％的一种或多种Li、Na、K、Rb和Ce以及0.005-0.5％的一种或多种Ni、Co和Te。这样此类粉末中至少含六种合金元素，更重要的是它是汞齐化的。JP-A-62176053 discloses an amalgamated zinc powder containing 0.001-0.5% In, 0.005-0.5% Pb, 0.005-0.5% Al, 0.005-0.5% of one or more of Tl, Sn, Cd and Ga, 0.0001-0.5% of one or more of Li, Na, K, Rb and Ce and 0.005-0.5% of one or more of Ni, Co and Te. This type of powder contains at least six alloying elements, and more importantly, it is amalgamated.

从EP-A-0384975中已知含锂的锌合金，用作为Leclanche电池的杯体(cup)。锂的加入是为了改进机械强度，此特性对于碱性电池锌粉而言是没有意义的。Lithium-containing zinc alloys are known from EP-A-0384975 as cups for Leclanche batteries. Lithium is added to improve mechanical strength, a property that is meaningless for alkaline battery zinc powder.

本发明优选的粉末组成叙述在附在后面的权利要求2-22中。Preferred powder compositions according to the invention are described in the appended claims 2-22.

一种简便地生产本发明粉末的方法，包括将所有应存在于粉末的添加剂(Al和例如In和Bi)加入到熔融的锌中，而后用气、水或其混合物将所得的合金雾化。生产者也可以雾化已含部分添加剂(例如Al和Bi)的熔融锌，而后将其余的添加剂沉淀在雾化的粉末上，这可以通过从一种水溶液中置换沉淀而得，也可以通过物理气相淀积(PVD)或通过化学气相淀积(CVD)的方法而实现。很显然，只有当添加剂的正电性大于锌才能应用置换沉淀技术。当有多种添加剂需要沉积在雾化的粉末上，它们可以单独或一起淀积上去。A simple method of producing the powder of the invention consists in adding all additives (Al and eg In and Bi) which should be present in the powder to molten zinc and atomizing the resulting alloy with gas, water or a mixture thereof. Producers can also atomize molten zinc that already contains some additives (such as Al and Bi) and then deposit the remaining additives on the atomized powder, which can be obtained by displacement precipitation from an aqueous solution or by physical Vapor deposition (PVD) or by chemical vapor deposition (CVD) method to achieve. Obviously, the displacement precipitation technique can be applied only when the additive is more electropositive than zinc. When multiple additives need to be deposited on the atomized powder, they can be deposited individually or together.

也可以先雾化熔融的锌，而后将所有添加剂沉淀到粉末上去。It is also possible to atomize the molten zinc first and then deposit all additives onto the powder.

还可以将某一种添加剂部分地与熔融锌合金化的方法引入，而剩余的部分沉积到雾化的粉末上。It is also possible to introduce an additive by partially alloying it with the molten zinc, while the remainder is deposited on the atomized powder.

除了用气体、水或这两者的混合物进行雾化作用外，其它任何一种适于将熔融金属转化为粉末的技术均可采用，例如离心雾化或浇铸金属的浇铸和碾磨。In addition to atomization with gas, water or a mixture of the two, any other technique suitable for converting molten metal to powder may be used, such as centrifugal atomization or casting and grinding of cast metals.

在所需的粉末含有能置换沉淀的添加剂(例如In)时，则还有另一种生产粉末的方法，它包括应用上述任何一种方法制备内含不能置换沉淀的添加剂以及可选择性地加入部分能进行置换沉淀的添加剂的粉末，而后用制得的粉末生产一种阳极。将阳极引入到电池中，将能置换沉积的添加剂加到电池的电解质中，从那里它们置换淀积到阳极粉末上。When the desired powder contains additives that can displace precipitates (such as In), there is another method for producing powders that includes applying any of the above methods to prepare additives that contain non-displaceable precipitates and optionally adding A part of the additive powder capable of displacement precipitation is then used to produce an anode. The anode is introduced into the battery, and the displacement-depositable additives are added to the electrolyte of the battery, from where they are displacement-deposited onto the anode powder.

因此本发明不仅涉及一种被引入到电池中的粉末，而且还涉及一种存在于电池中的粉末。The invention therefore not only relates to a powder which is introduced into a battery, but also to a powder which is present in the battery.

                     实例1Instance 1

本实例将证明本发明的锌基粉末在电池部分放电后，在电池的电解质中具有优良的耐腐蚀性。This example will demonstrate the excellent corrosion resistance of the zinc-based powders of the present invention in the electrolyte of a battery after the battery has been partially discharged.

制备了七种粉末，其组成如下：除均含有Zn、500ppmPb、500ppmBi、500ppmIn外，这七种粉末分别含有0，5，7，16，21，70和280ppmAl。为获得这七种粉末，首先将所需量的合金元素加入到熔融状态的热致精炼的锌中。Seven kinds of powders were prepared, and their compositions were as follows: In addition to Zn, 500ppmPb, 500ppmBi, 500ppmIn, these seven kinds of powders contained 0, 5, 7, 16, 21, 70 and 280ppm Al respectively. To obtain these seven powders, the required amount of alloying elements is first added to thermally refined zinc in molten state.

这样生成的熔融体在450℃下通过搅拌使其均匀化。而后将熔融的合金流入压缩空气喷注中，这样就制成了合金粉末，其粒子也具有与均匀的熔融体相类似的基本同样均匀的组成。The melt thus produced was homogenized by stirring at 450°C. The molten alloy is then flowed into a compressed air jet, thus producing an alloy powder whose particles also have a substantially uniform composition similar to that of a homogeneous melt.

将合金粉末筛分以去除大于500μm的部分，并尽可能去除小于104μm的部分。通过这种方法得到了粒子尺寸在104到500μm的合金粉末。The alloy powder was sieved to remove parts larger than 500 μm and as much as possible to remove parts smaller than 104 μm. Alloy powders with particle sizes ranging from 104 to 500 μm were obtained by this method.

用此合金粉末制造LR-14-型电池。这些电池在2.2欧姆下放电2小时，而后在45℃下检测七天内逸出的氢气量。结果列于下表中。An LR-14-type battery was produced from this alloy powder. The cells were discharged for 2 hours at 2.2 ohms and then measured for the amount of hydrogen evolved over a period of seven days at 45°C. The results are listed in the table below.

          表    Al含量ppm 气体逸出速μl/g天率     057162170280     9645302010112 surface Al contentppm Gas escape rate μl/g day rate 057162170280 9645302010112

这些结果证明加入少量的Al就可以显著地降低气体逸出速率。These results demonstrate that adding a small amount of Al can significantly reduce the gas evolution rate.

                     实例2Example 2

本实例将证明本发明的锌基粉末在电池部分放电后在电池的电解质中具有优良的耐腐蚀性。This example will demonstrate the excellent corrosion resistance of the zinc-based powders of the present invention in the electrolyte of the battery after the battery has been partially discharged.

制备除均含有Zn、500ppmIn和500ppmBi外分别含0、35和70ppmAl三种不同组成的粉末。此后按照实例1的方法继续进行。The powders containing three different compositions of 0, 35 and 70ppm Al were prepared except Zn, 500ppmIn and 500ppmBi. Thereafter proceed according to the method of example 1.

用这些合金粉末制造LR-14-型电池。这些电池在2.2欧姆下放电9小时。而后在71℃下检测七天内逸出的氢气。结果分别为165、101和73μl/g天。LR-14-type batteries were produced using these alloy powders. These cells were discharged for 9 hours at 2.2 ohms. The hydrogen evolution was then detected at 71°C for seven days. The results were 165, 101 and 73 μl/g day, respectively.

                    实例3Example 3

此实例将证明本发明的锌基粉末在LR6-型电池中不引起短路。This example will demonstrate that the zinc-based powders of the present invention do not cause short circuits in LR6-type batteries.

制备除均含有Zn、500ppmIn和500ppmBi外分别含30、70和325ppmAl的三种粉末，此后按实例1的方法继续进行。Prepare three kinds of powders containing 30, 70 and 325 ppm Al respectively except that all contain Zn, 500 ppm In and 500 ppm Bi, and proceed as in Example 1 thereafter.

这些粉末提供给电池制造者，用于LR6-型电池中。他们告诉本申请人含325ppmAl的粉末不适于此型电池因为会引起短路，而含30和70ppmAl的粉末适合，因为在相同型号的电池中未出现短路问题。These powders are supplied to battery manufacturers for use in LR6-type batteries. They told the applicant that a powder containing 325 ppm Al was not suitable for this type of cell because it would cause short circuits, whereas a powder containing 30 and 70 ppm Al was suitable because no short circuit problems occurred in cells of the same type.

本发明其他典型的粉末实例具有如下组成：Other typical powder examples of the present invention have the following composition:

      Zn-30ppmAl-250ppmBiZn-30ppmAl-250ppmBi

      Zn-40ppmAl-250ppmBiZn-40ppmAl-250ppmBi

      Zn-70ppmAl-250ppmBiZn-70ppmAl-250ppmBi

      Zn-85ppmAl-250ppmBiZn-85ppmAl-250ppmBi

   5  Zn-30ppmAl-250ppmBi-180ppmCa5 Zn-30ppmAl-250ppmBi-180ppmCa

      Zn-70ppmAl-250ppmBi-250ppmCaZn-70ppmAl-250ppmBi-250ppmCa

      Zn-30ppmAl-250ppmBi-45ppmCaZn-30ppmAl-250ppmBi-45ppmCa

      Zn-70ppmAl-250ppmBi-100ppmCaZn-70ppmAl-250ppmBi-100ppmCa

      Zn-30ppmAl-250ppmBi-180ppmPbZn-30ppmAl-250ppmBi-180ppmPb

  10  Zn-70ppmAl-250ppmBi-25ppmPb10 Zn-70ppmAl-250ppmBi-25ppmPb

      Zn-30ppmAl-500ppmBiZn-30ppmAl-500ppmBi

      Zn-40ppmAl-500ppmBiZn-40ppmAl-500ppmBi

      Zn-70ppmAl-500ppmBiZn-70ppmAl-500ppmBi

      Zn-30ppmAl-500ppmBi-180ppmCaZn-30ppmAl-500ppmBi-180ppmCa

  15  Zn-30ppmAl-1000ppmBi15 Zn-30ppmAl-1000ppmBi

      Zn-40ppmAl-1000ppmBiZn-40ppmAl-1000ppmBi

      Zn-70ppmAl-1000ppmBiZn-70ppmAl-1000ppmBi

      Zn-30ppmAl-1000ppmBi-180ppmCaZn-30ppmAl-1000ppmBi-180ppmCa

    Zn-40ppmAl-2300ppmBi20    Zn-70ppmAl-2300ppmBiZn-40ppmAl-2300ppmBi20 Zn-70ppmAl-2300ppmBi

    Zn-70ppmAl-3000ppmBiZn-70ppmAl-3000ppmBi

    Zn-40ppmAl-250ppmInZn-40ppmAl-250ppmIn

    Zn-70ppmAl-250ppmInZn-70ppmAl-250ppmIn

    Zn-40ppmAl-500ppmIn25    Zn-70ppmAl-500ppmInZn-40ppmAl-500ppmIn25 Zn-70ppmAl-500ppmIn

    Zn-40ppmAl-250ppmIn-200ppmCaZn-40ppmAl-250ppmIn-200ppmCa

    Zn-70ppmAl-250ppmIn-200ppmCaZn-70ppmAl-250ppmIn-200ppmCa

    Zn-40ppmAl-500ppmIn-200ppmCaZn-40ppmAl-500ppmIn-200ppmCa

    Zn-70ppmAl-500ppmIn-200ppmCa30    Zn-30ppmAl-2300ppmBi-180ppmCaZn-70ppmAl-500ppmIn-200ppmCa30 Zn-30ppmAl-2300ppmBi-180ppmCa

    Zn-30ppmAl-3000ppmBi-180ppmCaZn-30ppmAl-3000ppmBi-180ppmCa

    Zn-30ppmAl-250ppmIn-250ppmBiZn-30ppmAl-250ppmIn-250ppmBi

    Zn-40ppmAl-250ppmIn-250ppmBiZn-40ppmAl-250ppmIn-250ppmBi

    Zn-70ppmAl-250ppmIn-250ppmBi35    Zn-30ppmAl-500ppmIn-250ppmBiZn-70ppmAl-250ppmIn-250ppmBi35 Zn-30ppmAl-500ppmIn-250ppmBi

    Zn-40ppmAl-500ppmIn-250ppmBiZn-40ppmAl-500ppmIn-250ppmBi

    Zn-70ppmAl-500ppmIn-250ppmBiZn-70ppmAl-500ppmIn-250ppmBi

    Zn-30ppmAl-500ppmIn-500ppmBiZn-30ppmAl-500ppmIn-500ppmBi

    Zn-40ppmAl-500ppmIn-500ppmBi40    Zn-70ppmAl-500ppmIn-500ppmBiZn-40ppmAl-500ppmIn-500ppmBi40 Zn-70ppmAl-500ppmIn-500ppmBi

    Zn-30ppmAl-500ppmIn-1000ppmBiZn-30ppmAl-500ppmIn-1000ppmBi

    Zn-40ppmAl-500ppmIn-1000ppmBiZn-40ppmAl-500ppmIn-1000ppmBi

    Zn-70ppmAl-500ppmIn-1000ppmBiZn-70ppmAl-500ppmIn-1000ppmBi

    Zn-40ppmAl-500ppmIn-2300ppmBi45    Zn-70ppmAl-500ppmIn-2300ppmBiZn-40ppmAl-500ppmIn-2300ppmBi45 Zn-70ppmAl-500ppmIn-2300ppmBi

    Zn-70ppmAl-500ppmIn-3000ppmBiZn-70ppmAl-500ppmIn-3000ppmBi

    Zn-20ppmAl-500ppmIn-1000ppmBiZn-20ppmAl-500ppmIn-1000ppmBi

    Zn-40ppmAl-500ppmIn-1000ppmBi-50ppmPbZn-40ppmAl-500ppmIn-1000ppmBi-50ppmPb

    Zn-70ppmAl-500ppmIn-1000ppmBi-50ppmPb50  Zn-40ppmAl-500ppmIn-500ppmBi-50ppmPbZn-70ppmAl-500ppmIn-1000ppmBi-50ppmPb50 Zn-40ppmAl-500ppmIn-500ppmBi-50ppmPb

Zn-70ppmAl-500ppmIn-500ppmBi-50ppmPbZn-70ppmAl-500ppmIn-500ppmBi-50ppmPb

Zn-40ppmAl-250ppmIn-250ppmBi-100ppmPbZn-40ppmAl-250ppmIn-250ppmBi-100ppmPb

Zn-250ppmLi-250ppmBiZn-250ppmLi-250ppmBi

Zn-430ppmLi-250ppmBi55  Zn-30ppmLi-250ppmBi-100ppmPbZn-430ppmLi-250ppmBi55 Zn-30ppmLi-250ppmBi-100ppmPb

Zn-50ppmLi-250ppmBi-250ppmPbZn-50ppmLi-250ppmBi-250ppmPb

Zn-30ppmLi-500ppmBiZn-30ppmLi-500ppmBi

Zn-50ppmLi-500ppmBiZn-50ppmLi-500ppmBi

Zn-250ppmLi-500ppmBi60  Zn-430ppmLi-500ppmBiZn-250ppmLi-500ppmBi60 Zn-430ppmLi-500ppmBi

Zn-50ppmLi-500ppmBi-200ppmCaZn-50ppmLi-500ppmBi-200ppmCa

Zn-250ppmLi-500ppmBi-100ppmCaZn-250ppmLi-500ppmBi-100ppmCa

Zn-30ppmLi-500ppmInZn-30ppmLi-500ppmIn

Zn-50ppmLi-500ppmIn65  Zn-250ppmLi-500ppmInZn-50ppmLi-500ppmIn65 Zn-250ppmLi-500ppmIn

Zn-430ppmLi-500ppmInZn-430ppmLi-500ppmIn

Zn-50ppmLi-500ppmIn-200ppmCaZn-50ppmLi-500ppmIn-200ppmCa

Zn-250ppmLi-500ppmIn-100ppmCaZn-250ppmLi-500ppmIn-100ppmCa

Zn-250ppmLi-1000ppmIn70  Zn-430ppmLi-1000ppmInZn-250ppmLi-1000ppmIn70 Zn-430ppmLi-1000ppmIn

Zn-50ppmLi-1000ppmIn-200ppmCaZn-50ppmLi-1000ppmIn-200ppmCa

Zn-250ppmLi-2300ppmBiZn-250ppmLi-2300ppmBi

Zn-430ppmLi-2300ppmBiZn-430ppmLi-2300ppmBi

Zn-50ppmLi-3000ppmBi75  Zn-30ppmLi-3000ppmBiZn-50ppmLi-3000ppmBi75 Zn-30ppmLi-3000ppmBi

Zn-50ppmLi-2300ppmBi-200ppmCaZn-50ppmLi-2300ppmBi-200ppmCa

Zn-250ppmLi-250ppmBi-500ppmInZn-250ppmLi-250ppmBi-500ppmIn

Zn-430ppmLi-250ppmBi-500ppmInZn-430ppmLi-250ppmBi-500ppmIn

Zn-30ppmLi-250ppmBi-500ppmIn-100ppmPb80  Zn-50ppmLi-250ppmBi-500ppmIn-250ppmPbZn-30ppmLi-250ppmBi-500ppmIn-100ppmPb80 Zn-50ppmLi-250ppmBi-500ppmIn-250ppmPb

Zn-30ppmLi-500ppmBi-500ppmInZn-30ppmLi-500ppmBi-500ppmIn

 Zn-50ppmLi-500ppmBi-500ppmInZn-50ppmLi-500ppmBi-500ppmIn

 Zn-250ppmLi-500ppmBi-500ppmInZn-250ppmLi-500ppmBi-500ppmIn

 Zn-430ppmLi-500ppmBi-500ppmIn85   Zn-50ppmLi-500ppmBi-500ppmIn-200ppmCaZn-430ppmLi-500ppmBi-500ppmIn85 Zn-50ppmLi-500ppmBi-500ppmIn-200ppmCa

 Zn-253ppmLi-500ppmBi-500ppmIn-100ppmCaZn-253ppmLi-500ppmBi-500ppmIn-100ppmCa

 Zn-30ppmLi-1000ppmBi-500ppmInZn-30ppmLi-1000ppmBi-500ppmIn

 Zn-50ppmLi-1000ppmBi-500ppmInZn-50ppmLi-1000ppmBi-500ppmIn

 Zn-250ppmLi-1000ppmBi-500ppmIn90   Zn-430ppmLi-1000ppmBi-500ppmInZn-250ppmLi-1000ppmBi-500ppmIn90 Zn-430ppmLi-1000ppmBi-500ppmIn

 Zn-30ppmAl-30ppmLi-250ppmBiZn-30ppmAl-30ppmLi-250ppmBi

 Zn-30ppmAl-50ppmLi-250ppmBiZn-30ppmAl-50ppmLi-250ppmBi

 Zn-70ppmAl-30ppmLi-250ppmBiZn-70ppmAl-30ppmLi-250ppmBi

 Zn-70ppmAl-50ppmLi-250ppmBi95   Zn-30ppmAl-30ppmLi-250ppmBi-180ppmCaZn-70ppmAl-50ppmLi-250ppmBi95 Zn-30ppmAl-30ppmLi-250ppmBi-180ppmCa

 Zn-70ppmAl-30ppmLi-250ppmBi-250ppmCaZn-70ppmAl-30ppmLi-250ppmBi-250ppmCa

 Zn-30ppmAl-250ppmLi-250ppmBiZn-30ppmAl-250ppmLi-250ppmBi

 Zn-70ppmAl-250ppmLi-250ppmBiZn-70ppmAl-250ppmLi-250ppmBi

 Zn-30ppmAl-50ppmLi-250ppmBi-180ppmPb100  Zn-70ppmAl-30ppmLi-250ppmBi-250ppmPbZn-30ppmAl-50ppmLi-250ppmBi-180ppmPb100 Zn-70ppmAl-30ppmLi-250ppmBi-250ppmPb

 Zn-30ppmAl-30ppmLi-500ppmBiZn-30ppmAl-30ppmLi-500ppmBi

 Zn-30ppmAl-50ppmLi-500ppmBiZn-30ppmAl-50ppmLi-500ppmBi

 Zn-70ppmAl-50ppmLi-500ppmBiZn-70ppmAl-50ppmLi-500ppmBi

 Zn-30ppmAl-250ppmLi-500ppmBi105  Zn-30ppmAl-30ppmLi-1000ppmBiZn-30ppmAl-250ppmLi-500ppmBi105 Zn-30ppmAl-30ppmLi-1000ppmBi

 Zn-30ppmAl-250ppmLi-1000ppmBiZn-30ppmAl-250ppmLi-1000ppmBi

 Zn-70ppmAl-30ppmLi-1000ppmBiZn-70ppmAl-30ppmLi-1000ppmBi

 Zn-30ppmAl-250ppmLi-2300ppmBiZn-30ppmAl-250ppmLi-2300ppmBi

 Zn-70ppmAl-30ppmLi-2300ppmBi110  Zn-70ppmAl-50ppmLi-3000ppmBiZn-70ppmAl-30ppmLi-2300ppmBi110 Zn-70ppmAl-50ppmLi-3000ppmBi

 Zn-30ppmAl-50ppmLi-250ppmInZn-30ppmAl-50ppmLi-250ppmIn

 Zn-70ppmAl-50ppmLi-250ppmInZn-70ppmAl-50ppmLi-250ppmIn

 Zn-30ppmAl-30ppmLi-500ppmInZn-30ppmAl-30ppmLi-500ppmIn

  Zn-70ppmAl-30ppmLi-500ppmIn115   Zn-30ppmAl-30ppmLi-250ppmIn-250ppmBiZn-70ppmAl-30ppmLi-500ppmIn115 Zn-30ppmAl-30ppmLi-250ppmIn-250ppmBi

  Zn-30ppmAl-50ppmLi-250ppmIn-250ppmBiZn-30ppmAl-50ppmLi-250ppmIn-250ppmBi

  Zn-70ppmAl-30ppmLi-250ppmIn-250ppmBiZn-70ppmAl-30ppmLi-250ppmIn-250ppmBi

  Zn-30ppmAl-250ppmLi-250ppmIn-250ppmBiZn-30ppmAl-250ppmLi-250ppmIn-250ppmBi

  Zn-30ppmAl-30ppmLi-500ppmIn-250ppmBi120   Zn-30ppmAl-50ppmLi-500ppmIn-250ppmBiZn-30ppmAl-30ppmLi-500ppmIn-250ppmBi120 Zn-30ppmAl-50ppmLi-500ppmIn-250ppmBi

  Zn-70ppmAl-30ppmLi-500ppmIn-250ppmBiZn-70ppmAl-30ppmLi-500ppmIn-250ppmBi

  Zn-30ppmAl-250ppmLi-500ppmIn-250ppmBiZn-30ppmAl-250ppmLi-500ppmIn-250ppmBi

  Zn-30ppmAl-50ppmLi-500ppmIn-500ppmBiZn-30ppmAl-50ppmLi-500ppmIn-500ppmBi

  Zn-30ppmAl-250ppmLi-500ppmIn-500ppmBi125   Zn-70ppmAl-50ppmLi-500ppmIn-500ppmBiZn-30ppmAl-250ppmLi-500ppmIn-500ppmBi125 Zn-70ppmAl-50ppmLi-500ppmIn-500ppmBi

  Zn-30ppmAl-30ppmLi-500ppmIn-1000ppmBiZn-30ppmAl-30ppmLi-500ppmIn-1000ppmBi

  Zn-30ppmAl-250ppmLi-500ppmIn-1000ppmBiZn-30ppmAl-250ppmLi-500ppmIn-1000ppmBi

  Zn-70ppmAl-30ppmLi-500ppmIn-1000ppmBiZn-70ppmAl-30ppmLi-500ppmIn-1000ppmBi

  Zn-70ppmAl-50ppmLi-500ppmIn-1000ppmBi130   Zn-30ppmAl-50ppmLi-500ppmIn-2300ppmBiZn-70ppmAl-50ppmLi-500ppmIn-1000ppmBi130 Zn-30ppmAl-50ppmLi-500ppmIn-2300ppmBi

  Zn-70ppmAl-30ppmLi-500ppmIn-2300ppmBiZn-70ppmAl-30ppmLi-500ppmIn-2300ppmBi

  Zn-70ppmAl-30ppmLi-500ppmIn-3000ppmBiZn-70ppmAl-30ppmLi-500ppmIn-3000ppmBi

这些粉末除锌和不可避免的杂质外，仅含给定的添加物，不可避免的杂质指那些存在于锌及添加物之中的杂质。These powders contain only the given additions in addition to zinc and unavoidable impurities, which are those present in the zinc and the additions.

Claims (24)

  1. One kind be used for alkaline cell contain the aluminium zinc powder, it is characterized in that its contain 1-95ppm Al and
    Or also contain 0.001-2%Bi, 0.005-2%In and 0.003-2%Pb, and the optional 0.003-2%Ca that contains;
    Or contain 0.001-2%Bi and 0.005-2%In; And the optional 0.003-2%Pb that contains;
    Or contain a kind of among 0.001-2%Bi and the 0.005-2%In; 0.003-2%Pb, and the optional 0.003-2%Ca that contains;
    Remaining then is zinc and be present in unavoidable impurities in the above-mentioned metal, unless but calcic otherwise contain the indium powder with what eliminating contained 50ppm aluminium.
  2. One kind be used for alkaline cell contain the lithium zinc powder, it is characterized in that its contain the 1-1000ppm lithium and
    Or contain at least a among 0.001-2%Bi and the 0.005-2%In, and the optional 0.003-2%Ca that contains;
    Or contain 0.003-2%Pb, 0.003-2%Ca, and the optional 0.005-2%In that contains;
    Or contain 0.001-2%Bi, 0.003-2%Pb, and optional contain at least a among 0.005-2%In and the 0.003-2%Ca;
    Remaining is for zinc and be present in unavoidable impurities in the above-mentioned metal.
  3. 3. a zinc powder that contains aluminium and lithium that is used for alkaline cell is characterized in that it contains 1-95ppmAl; 1-1000ppmLi; At least a among 0.001-2%Bi, 0.005-2%In and the 0.003-2%Pb, and the optional 0.003-2%Ca that contains, remaining is then for zinc and be present in unavoidable impurities in the above-mentioned metal.
  4. 4. according to the powder of claim 1 or 3, it is characterized in that it contains 1-85ppmAl.
  5. 5. according to the powder of claim 4, it is characterized in that it contains 1-45ppmAl.
  6. 6. according to the powder of claim 5, it is characterized in that it contains 5-45ppmAl.
  7. 7. according to arbitrary powder among the claim 2-6, it is characterized in that it contains 5-500ppmLi.
  8. 8. according to the powder of claim 7, it is characterized in that it contains 10-200ppmLi.
  9. 9. according to arbitrary powder among the claim 1-8, it is characterized in that it contains 0.003-0.3%Bi.
  10. 10. according to the powder of claim 9, it is characterized in that it contains 0.003-0.2%Bi.
  11. 11., it is characterized in that it contains 0.003-0.1%Bi according to the powder of claim 10.
  12. 12., it is characterized in that only containing Bi and at least a Al and Li as alloying element according to arbitrary powder among the claim 1-11.
  13. 13., it is characterized in that only containing Bi, Ca and at least a Al and Li as alloying element according to arbitrary powder among the claim 1-11.
  14. 14., it is characterized in that only containing In, Bi and at least a Al and Li as alloying element according to arbitrary powder among the claim 1-11.
  15. 15., it is characterized in that only containing In, Bi, Li, Ca and optional Al as alloying element according to arbitrary powder among the claim 1-11.
  16. 16., it is characterized in that only containing Pb, Bi and at least a Al and Li as alloying element according to arbitrary powder among the claim 1-11.
  17. 17., it is characterized in that only containing Pb, Bi, Ca and at least a Al and Li as alloying element according to arbitrary powder among the claim 1-11.
  18. 18., it is characterized in that only containing Pb, Bi, In and at least a Al and Li as alloying element according to arbitrary powder among the claim 1-11.
  19. 19., it is characterized in that only containing Pb, Bi, In, Li, Ca and optional Al as alloying element according to arbitrary powder among the claim 1-11.
  20. 20., it is characterized in that it contains 0.01-0.1%In according to arbitrary powder among the claim 1-11,14,15,18 and 19.
  21. 21., it is characterized in that it contains 0.01-0.1%Pb according to arbitrary powder among claim 1-11 and the 16-19.
  22. 22., it is characterized in that it contains 0.05-0.1%Ca according to arbitrary powder among the claim 1-11,13,15,17 and 19.
  23. 23. comprise anode, negative electrode and electrolytical alkaline cell, it is characterized in that this anode contains among the with good grounds claim 1-22 arbitrary powder that makes as active substance.
  24. 24., it is characterized in that this powder contains the metal that the displacement deposit goes out from ionogen according to the alkaline cell of claim 23.
CN94191302A 1993-02-25 1994-02-16 Zinc powder for alkaline batteries Expired - Lifetime CN1045999C (en)

Applications Claiming Priority (2)

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BE9300178A BE1007443A3 (en) 1993-02-25 1993-02-25 Zinc powder for alkaline batteries.
BE09300178 1993-02-25

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CN1118610A true CN1118610A (en) 1996-03-13
CN1045999C CN1045999C (en) 1999-10-27

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JP (1) JPH08510010A (en)
CN (1) CN1045999C (en)
AU (1) AU6141194A (en)
BE (1) BE1007443A3 (en)
CA (1) CA2153330C (en)
DE (1) DE69424157T2 (en)
ES (1) ES2147783T3 (en)
LT (1) LT3232B (en)
WO (1) WO1994019502A1 (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1960031B (en) * 2005-11-02 2011-02-02 日立麦克赛尔株式会社 Alkaline battery
CN104972108A (en) * 2015-07-07 2015-10-14 江苏冶建锌业有限公司 Ultrafine zinc alloy powder and preparation method thereof
CN104988353A (en) * 2015-07-07 2015-10-21 江苏冶建锌业有限公司 Cadmium-free lead-free super-fine zinc alloy powder and preparation method thereof
CN109536778A (en) * 2017-12-05 2019-03-29 袁丹 A kind of medical degradable zinc bismuth lithium system alloy

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EP0883903B1 (en) * 1996-02-22 2006-06-07 Umicore Process for manufacturing a primary zinc-alkaline battery and anode mix used therein
JP3617743B2 (en) * 1996-10-09 2005-02-09 同和鉱業株式会社 Negative electrode material for alkaline manganese battery and method for producing the same
KR100624305B1 (en) * 1999-02-09 2006-09-13 유미코르 Centrifugal Atomized Zinc Alloy Powder for Alkaline Battery
US20070264572A1 (en) 2006-05-09 2007-11-15 Zuraw Michael J Battery Anodes
JP2009064756A (en) 2007-09-10 2009-03-26 Panasonic Corp Alkaline battery
US9105923B2 (en) 2013-02-13 2015-08-11 Nanophase Technologies Corporation Zinc anode alkaline electrochemical cells containing bismuth

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JPS61193362A (en) * 1985-02-21 1986-08-27 Mitsui Mining & Smelting Co Ltd Zinc alkaline battery
JPH0628160B2 (en) * 1986-01-29 1994-04-13 三井金属鉱業株式会社 Zinc alkaline battery
DE3902650A1 (en) * 1989-01-30 1990-08-02 Varta Batterie GALVANIC PRIME ELEMENT
BE1003415A6 (en) * 1989-11-10 1992-03-17 Acec Union Miniere Zinc powder for alkaline batteries.
US5168018A (en) * 1990-05-17 1992-12-01 Matsushita Electric Industrial Co., Ltd. Method of manufacturing zinc-alkaline batteries
JP2808822B2 (en) * 1990-05-17 1998-10-08 松下電器産業株式会社 Manufacturing method of zinc alkaline battery
JPH0754704B2 (en) * 1991-02-19 1995-06-07 三井金属鉱業株式会社 Zinc alloy powder for alkaline battery and method for producing the same
JP3111634B2 (en) * 1992-05-25 2000-11-27 松下電器産業株式会社 Manufacturing method of zinc alkaline battery
JP3553104B2 (en) * 1992-08-04 2004-08-11 株式会社エスアイアイ・マイクロパーツ Alkaline battery

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1960031B (en) * 2005-11-02 2011-02-02 日立麦克赛尔株式会社 Alkaline battery
CN104972108A (en) * 2015-07-07 2015-10-14 江苏冶建锌业有限公司 Ultrafine zinc alloy powder and preparation method thereof
CN104988353A (en) * 2015-07-07 2015-10-21 江苏冶建锌业有限公司 Cadmium-free lead-free super-fine zinc alloy powder and preparation method thereof
CN104988353B (en) * 2015-07-07 2017-01-11 江苏冶建锌业有限公司 Cadmium-free lead-free super-fine zinc alloy powder and preparation method thereof
CN109536778A (en) * 2017-12-05 2019-03-29 袁丹 A kind of medical degradable zinc bismuth lithium system alloy

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LT3232B (en) 1995-04-25
CA2153330C (en) 1999-09-28
EP0686207B1 (en) 2000-04-26
LTIP1881A (en) 1994-10-25
DE69424157T2 (en) 2000-12-14
AU6141194A (en) 1994-09-14
DE69424157D1 (en) 2000-05-31
ES2147783T3 (en) 2000-10-01
JPH08510010A (en) 1996-10-22
CA2153330A1 (en) 1994-09-01
CN1045999C (en) 1999-10-27
WO1994019502A1 (en) 1994-09-01
BE1007443A3 (en) 1995-07-04
EP0686207A1 (en) 1995-12-13

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